CN109065700B - Preparation method of annular thermoelectric power generation device - Google Patents
Preparation method of annular thermoelectric power generation device Download PDFInfo
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- CN109065700B CN109065700B CN201810783615.4A CN201810783615A CN109065700B CN 109065700 B CN109065700 B CN 109065700B CN 201810783615 A CN201810783615 A CN 201810783615A CN 109065700 B CN109065700 B CN 109065700B
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Abstract
The invention relates to a preparation method of an annular thermoelectric power generation device, which comprises the following steps: coating soldering flux on two end faces of the p-type thermoelectric element and the n-type thermoelectric element for bonding soldering lugs; after the annular tray is placed on the convex base, the inner ring electrodes are distributed on the annular tray and abut against the bosses of the convex base; one end faces of the p-type thermoelectric elements and the n-type thermoelectric elements are alternatively and circularly abutted against the inner ring electrode according to the p-type thermoelectric elements and the n-type thermoelectric elements; the outer ring electrode is abutted against the other end faces of the p-type thermoelectric element and the n-type thermoelectric element and is arranged in a staggered manner with the inner ring electrode; pushing the clamping ring from the edge of the boss base to the outer ring electrode, so that the clamping ring presses the outer ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the inner ring electrode to complete the assembly of the annular thermoelectric power generation device; and heating the soldering lug to obtain the annular thermoelectric power generation device.
Description
Technical Field
The invention relates to a preparation method of a non-planar heat source thermoelectric power generation device, in particular to a preparation method of an annular thermoelectric power generation device, and belongs to the technical field of thermoelectric power generation.
Background
The thermoelectric power generation technology utilizes the Seebeck effect of a semiconductor material to directly convert heat energy into electric energy, has the characteristics of small system volume, compact structure, no movable part, no maintenance, no noise, no emission, high reliability, long service life and the like, is important applied to deep space exploration power supplies and special military power supplies, has wide application prospect and potential economic and social benefits in the aspects of solar photoelectric-thermoelectric composite power generation and industrial waste heat, particularly in the aspect of recovering thermoelectric power generation from automobile exhaust waste heat, and can possibly become an important component of the current world energy crisis solution (T.M.Tritt, thermoelectric materials-Holey and uney semiconductor, Science 283:804,1999).
The thermoelectric device is a key component of a thermoelectric power generation system, and is generally composed of a plurality of p-type thermoelectric elements and n-type semiconductor thermoelectric elements. Since the output voltage of a single thermoelectric element is low, in order to obtain a sufficiently high voltage for practical use, a p-type thermoelectric element and an n-type thermoelectric element are often connected by using metal or alloy electrodes to form a thermoelectric single couple (or a pi-shaped thermoelectric element), and then a plurality of thermoelectric single couples are connected in an electrically-conductive series-conductive and thermally-conductive parallel-connected structure to form a thermoelectric device.
A common thermoelectric device is a planar structure composed of a plurality of pairs of pi-shaped thermoelectric elements, as shown in fig. 1 (a). In this configuration, p-type and n-type thermoelectric elements are integrated in electrically and thermally conductive series and parallel between electrically and thermally insulating parallel ceramic plates with good thermal conductivity, and the thermoelectric device is suitable for use with planar heat sources, i.e., with the direction of heat flow perpendicular to the ceramic plates.
However, when the heat source is non-planar, such a conventional flat-plate module thermoelectric device is not suitable for use in, for example, exhaust gas discharge pipes of automobiles and aircrafts, and the circular arc surface of the conventional flat-plate module thermoelectric device is not only unfavorable for installation of the flat-plate module device, but also unfavorable for heat transfer to thermoelectric devices to establish temperature difference, which greatly affects the thermoelectric conversion efficiency of the thermoelectric device. In response to this problem, patents US2012/0174567a1, CN201420052870, CN201410846352, CN201410846295, CN201410626515, CN201410626099, CN201410039382 and CN201420052870, etc. disclose a thermoelectric generator structure (shown in (b) in fig. 1) integrated with a ring-shaped thermoelectric device, according to the design structure, the heat source can exchange heat with the thermoelectric element from the radial direction and the axial direction, and the heat exchange efficiency is obviously improved compared with the traditional generator integrated by pi-shaped devices.
Although the concept of the existing annular thermoelectric device well meets the application requirements of the exhaust gas emission pipeline, the practical application of the existing annular thermoelectric device still has some problems. The existing annular thermoelectric device can be suitable for a tubular heat source with a smaller diameter, and when the diameter of the heat source is larger, the practical application of the thermoelectric material preparation technology, the element processing technology, the device integration technology and the like of a large-size block body is restricted. For the heat sources with the diameters large enough and allowing improved design, a processing plane can be designed along the circumference of the heat source, and a flat thermoelectric device is adopted for heat recovery and power generation; however, for those heat sources with limited space and not allowed to be improved in design, such as waste heat of the unmanned jet nozzle, especially when the jet nozzle part is in a conical structure (fig. 2), the existing flat thermoelectric device and annular thermoelectric device cannot effectively perform tail gas waste heat recovery thermoelectric power generation, and a thermoelectric device with a novel structure needs to be developed. Although numerous documents (US6005182, US6759586, US6563039, CN1585145, US6005182, US6759586, US2008/0023057, US2006/0017170, US6563039, CN101447548, JP11195817, CN201410039382, CN201410846295, CN201410626099, AND semiconductor science technol.22:880-883,2007(Min Gao, d.m. rowe, Ring-structured thermoelectric module, secmiconctorscience AND techlogo 22:880-883,2007)) report the preparation methods of flat/annular thermoelectric devices, none of the existing thermoelectric device preparation technologies can be well used to prepare annular thermoelectric devices suitable for recycling of the above-mentioned complex heat sources, requiring development of new annular thermoelectric device preparation technologies.
Disclosure of Invention
In order to solve the problem of preparing the thermoelectric power generation device by recovering the waste heat of the complex heat source, the invention provides a preparation method of an annular thermoelectric power generation device, which comprises the following steps:
coating soldering flux on two end faces of the p-type thermoelectric element and the n-type thermoelectric element for bonding soldering lugs;
after the annular tray is placed on the convex base, the inner ring electrodes are distributed on the annular tray and abut against the bosses of the convex base;
one end faces of the p-type thermoelectric elements and the n-type thermoelectric elements are alternatively abutted against the inner ring electrode according to the p-type thermoelectric elements and the n-type thermoelectric elements;
the outer ring electrode is abutted against the other end faces of the p-type thermoelectric element and the n-type thermoelectric element and is arranged in a staggered manner with the inner ring electrode;
pushing the clamping ring from the edge of the boss base to the outer ring electrode, so that the clamping ring presses the outer ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the inner ring electrode to complete the assembly of the annular thermoelectric power generation device;
and heating the soldering lug to obtain the annular thermoelectric power generation device.
Preferably, the material of the p-type thermoelectric element and the n-type thermoelectric element is at least one of a bismuth telluride-based thermoelectric material, a lead telluride-based thermoelectric material, a transition metal oxide thermoelectric material, a half heusler thermoelectric material, a skutterudite-based thermoelectric material, a silicon-germanium-based thermoelectric material and a copper-based compound thermoelectric material.
Preferably, the p-type thermoelectric element and the n-type thermoelectric element are in a cube, a cuboid or an orthorhombic body, and the inclination angle of the orthorhombic body is determined by the taper of the heat source; the dimensions of the p-type thermoelectric element and the n-type thermoelectric element are (3-5 mm) × (2-5 mm).
Preferably, the angle of the inner ring electrode is 150 to 175 degrees, and the angle of the outer ring electrode is 150 to 175 degrees.
Preferably, the soldering lug is made of one of tin, gold, silver, copper, nickel, titanium and alloy thereof, and the thickness of the soldering lug is 50-150 μm.
Preferably, before coating the soldering flux, barrier layers are prepared on two end faces of the p-type thermoelectric element and the n-type thermoelectric element, the material of the barrier layers is at least one of Ni, Fe, Ti, Mo and Nb and alloys thereof, and the thickness of the barrier layers is 20-150 μm.
Preferably, the material of the inner ring electrode and the outer ring electrode is selected from at least one of copper, iron, nickel, chromium, cobalt, titanium, molybdenum, tungsten, niobium and the alloy thereof.
Preferably, a pressure ring is placed on the clamping ring, and the clamping ring is pressed against the outer ring electrode, the p-type and n-type thermoelectric elements, and the inner ring electrode by the weight of the pressure ring.
Preferably, the heating mode is resistance heating or induction heating.
On the other hand, in the invention, preferably, the upper part of the outer ring of the clamping ring is provided with a chamfer with an angle of 25-75 degrees; preferably, the clamping ring is divided into 3-8 petals.
In the disclosure, a plurality of p-type and n-type thermoelectric elements are used for surrounding a non-planar heat source, and the small plane is attached to the large plane, so that heat transmission and device arrangement are facilitated, the number of thermoelectric pairs of annular devices can be adjusted according to different diameters of the heat source, or the cross-sectional size of the thermoelectric elements can be changed, and therefore, the requirements of practical application are met, and the power generation efficiency and the output power density of the devices are improved. In addition, the annular thermoelectric power generation device is prepared by using the special die, the preparation method is simple, and the annular thermoelectric power generation device can be used for preparing the annular thermoelectric power generation device in a large scale so as to effectively recover waste heat of a heat source with a special structure to perform thermoelectric power generation and improve the utilization rate of energy.
Drawings
FIG. 1 is a prior art planar thermoelectric device (a) and a ring-type thermoelectric device (b);
FIG. 2 is a heat source of a particular shape;
fig. 3 is a schematic three-dimensional structure of a ring-shaped thermoelectric power generation device to which a conical heat source is applied in example 1 of the present invention;
fig. 4 is a schematic three-dimensional structure of an orthorhombic thermoelectric element of a circular thermoelectric power generation device suitable for a conical heat source in example 1 of the present invention;
fig. 5 is a schematic three-dimensional structure of an annular thermoelectric power generation device in example 2 of the present invention;
FIG. 6 is a schematic view of a thermoelectric single couple of a ring-shaped thermoelectric power generation device in example 2 of the present invention;
fig. 7 is a schematic flow chart of the process for preparing the annular thermoelectric power generation device.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In order to overcome the defects of the conventional thermoelectric device, the invention provides the annular thermoelectric power generation device with a novel structure so as to effectively recover the waste heat of a heat source with a special structure to carry out thermoelectric power generation.
In one embodiment of the present invention, the annular thermoelectric power generation device is in a non-closed annular state, which facilitates the serial and parallel connection of the devices to improve the output power and voltage of the thermoelectric power generation system, and the structure includes: a plurality of square, rectangular or rhombus p-type thermoelectric elements and n-type thermoelectric elements which are alternately distributed around, and electrodes for connecting the p-type thermoelectric elements and the n-type thermoelectric elements. Wherein, the electrodes are divided into an inner ring electrode and an outer ring electrode. Wherein the inner ring electrode and the outer ring electrode have a break angle in a direction along a center line between the p-type thermoelectric element and the n-type thermoelectric element (i.e., a middle in a length direction of the inner ring electrode and the outer ring electrode). The p-type thermoelectric elements and the n-type thermoelectric elements alternately surround a heat source, and the p-type thermoelectric elements and the n-type thermoelectric elements are sequentially and alternately connected through the inner ring electrodes and the outer ring electrodes to form a conductive series and heat conductive parallel structure.
In an alternative embodiment, the annular thermoelectric power generation device further comprises a barrier layer and a solder layer. In an alternative embodiment, a welding layer is further included between the inner ring electrode and the p-type thermoelectric element and the n-type thermoelectric element, the material of the welding layer may be at least one of tin, gold, silver, copper, nickel, titanium and alloys thereof, and the thickness may be 50-150 μm. In an alternative embodiment, a welding layer is further included between the outer ring electrode and the p-type thermoelectric element and the n-type thermoelectric element, the material of the welding layer may be at least one of tin, gold, silver, copper, nickel, titanium and alloys thereof, and the thickness may be 50-150 μm. In an alternative embodiment, a barrier layer is further included between the welding layer and the p-type thermoelectric element and the n-type thermoelectric element, the material of the barrier layer may be at least one of Ni, Fe, Ti, Mo and Nb and alloys thereof, and the thickness may be 20-150 μm.
In an alternative embodiment, the thermoelectric material of the p-type thermoelectric element and the n-type thermoelectric element constituting the ring-shaped thermoelectric power generation device includes: bismuth telluride (Bi)2Te3) The thermoelectric material can be selected according to the temperature of a heat source.
In an alternative embodiment, the electrodes of the annular thermoelectric power generation device are divided into an inner ring electrode and an outer ring electrode, the inner ring electrode and the outer ring electrode present a certain folding angle, and the size of the folding angle is determined according to the diameter of the annular power generation device and the size and the number of the thermoelectric elements so as to facilitate the electrodes and the thermoelectric elements to be tightly attached to a heat source. Generally, the angle of the inner ring electrode is 150 to 175 degrees, and the angle of the outer ring electrode is 150 to 175 degrees. The material of the electrode comprises metals such as copper, iron, nickel, chromium, cobalt, titanium, molybdenum, tungsten, niobium and the like, and alloys and composite materials thereof.
In alternative embodiments, the p-type thermoelectric elements and the n-type thermoelectric elements may be square, or rhombus in structure. When the p-type thermoelectric element and the n-type thermoelectric element are in an orthorhombic shape (see fig. 4), the inclination angles of the orthorhombic p-type thermoelectric element and the orthorhombic n-type thermoelectric element are determined by the taper of the heat source, and the p-type thermoelectric element and the n-type thermoelectric element are coupled to appear in pairs, as shown in fig. 6.
In an alternative embodiment, the p-type thermoelectric elements and the n-type thermoelectric elements have the same cross-sectional size, and the p-type thermoelectric elements and the n-type thermoelectric elements have the same height. The p-type thermoelectric elements and the n-type thermoelectric elements are alternately encircled into a ring and are in a structure of being mutually connected in series, so that a single-ring multi-pair series thermoelectric device is formed.
In an alternative embodiment, the ratio of the inner diameter of the annular thermoelectric power generation device to the length of the p-type thermoelectric element and the n-type thermoelectric element is greater than 10. The cross section of the p-type thermoelectric element and the n-type thermoelectric element refers to the surface connected with the inner ring electrode and the outer ring electrode, and the shape of the cross section is generally square. Generally, the inner ring of the annular thermoelectric power generation device is a high temperature end, and the outer ring is a low temperature end.
As an example of the structure of a ring-shaped thermoelectric power generating device, as shown in fig. 3, the ring-shaped thermoelectric power generating device includes: and a plurality of pairs of column-type p-type thermoelectric elements and n-type thermoelectric elements 2, outer ring guide electrodes 1 of each pair of p-type thermoelectric elements and n-type thermoelectric elements are connected to the outer side of the ring, and inner ring guide electrodes 3 of adjacent pairs of p-type thermoelectric elements and n-type thermoelectric elements are connected to the inner side of the ring in a manner of being interlaced with the outer ring guide electrodes.
In the present invention, the ring-shaped thermoelectric power generation device is in a non-closed ring-shaped state, and includes P-type thermoelectric elements and n-type thermoelectric elements alternately distributed in a ring shape, an inner ring electrode for connecting adjacent P-type thermoelectric elements and n-type thermoelectric elements to form thermoelectric pairs, and an outer ring electrode for connecting adjacent P-type thermoelectric elements and n-type thermoelectric elements in adjacent thermoelectric pairs, and it is possible to efficiently recover waste heat from a heat source having a special shape and perform thermoelectric power generation. The following exemplarily illustrates a method for manufacturing the ring-shaped thermoelectric power generating device, as shown in fig. 7. A mold for producing an annular thermoelectric power generating device, comprising: the clamping ring comprises a convex base, an annular tray matched with the convex base, a clamping ring and a pressing ring.
And preparing soldering flux and soldering lugs on two end faces of the p-type thermoelectric element and the n-type thermoelectric element. In an alternative embodiment, the p/n type thermoelectric element has a length × width × height (3 to 5mm) × (2 to 5 mm). The soldering lug comprises the following materials: tin, gold, silver, copper, nickel, titanium, and alloys thereof; the thickness of the soldering lug is 50-150 m. In an alternative embodiment, the thermoelectric material constituting the p-type, n-type thermoelectric element comprises: bismuth telluride (Bi)2Te3) The thermoelectric material comprises a base thermoelectric material, a lead telluride (PbTe) base thermoelectric material, a transition metal oxide thermoelectric material, a Half-Heusler (Half-Heusler) thermoelectric material, a Skutterudite (Skuttrudite) base thermoelectric material, a silicon germanium (SiGe) base thermoelectric material, a copper base compound thermoelectric material (such as copper-sulfur, copper-selenium, tetrahedrite and the like), a doped composite thermoelectric material thereof and a multi-stage thermoelectric material formed by the thermoelectric material. In addition, barrier layers can be added on the two end faces of the p-type thermoelectric element and the n-type thermoelectric element before the soldering flux is coated, the material of the barrier layers can be at least one of Ni, Fe, Ti, Mo and Nb and alloys thereof, and the thickness of the barrier layers can be 20-150 micrometers.
An annular tray is placed on the convex base. Wherein the shape and size of the boss of the convex base are consistent with the shape and size of the heat source. The convex base is made of cast iron, common steel, alloy steel, stainless steel, aluminum and alloy thereof, graphite and the like with good strength and thermal conductivity. The annular tray is matched with the convex base, and the annular tray is made of cast iron, common steel, alloy steel, stainless steel, aluminum, alloy thereof, graphite and the like with good strength and thermal conductivity.
And the inner ring electrode is abutted against the boss of the convex base and uniformly distributed on the annular tray, and the end faces of the P-type thermoelectric element and the n-type thermoelectric element are alternatively abutted against the inner ring electrode according to a P type/n type/P type and uniformly distributed on the annular tray.
And the outer ring electrode is abutted against the other end faces of the p-type thermoelectric element and the n-type thermoelectric element and is uniformly distributed on the annular tray in a staggered manner with the inner ring electrode. According to the invention, the materials adopted by the inner ring electrode and the outer ring electrode comprise: the electrode material comprises metals such as copper, iron, nickel, chromium, cobalt, titanium, molybdenum, tungsten, niobium and the like, and alloys and composite materials thereof; the inner ring electrode and the outer ring electrode present certain folding angles according to the diameter of the annular thermoelectric device, and the folding angle ranges are as follows: 150-175 degrees.
And pushing the clamping ring from the edge of the boss base to the outer ring electrode, so that the clamping ring is pressed against the outer ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the inner ring electrode to complete the assembly of the annular thermoelectric power generation device. In an optional embodiment, the upper part of the outer ring of the fastening ring is provided with a chamfer angle, and the angle is 25-75 degrees; preferably, the clamping ring is divided into 3-8 petals, so that the operation is convenient. In an alternative embodiment, a pressure ring is placed on the clamping ring, and the assembly of the annular thermoelectric power generation device is completed by the weight of the pressure ring. The inner circle radius of the clamping ring may be the sum of the radius of the convex heat source, the height of the thermoelectric element, and the thickness of the inner ring electrode and the outer ring electrode. The material used for the clamp ring may include cast iron, plain steel, alloy steel, stainless steel, aluminum and its alloys, graphite, etc., which are excellent in strength and thermal conductivity. The clamping ring is matched with the clamping ring, and the material used for the clamping ring can comprise cast iron, common steel, alloy steel, stainless steel and the like with good strength and thermal conductivity.
And heating the soldering lug to obtain the annular thermoelectric power generation device. Wherein, the heating device can adopt a heating platform, a muffle furnace, a vacuum heating furnace and the like. The heating may be by resistance heating or induction heating. Preferably, the induction heating means may include: medium frequency, high frequency, audio, etc.
As an example of a method for manufacturing a ring-shaped thermoelectric power generation device, the method includes: (1) coating a layer of soldering flux on the upper end surface and the lower end surface of the p-type thermoelectric element and the n-type thermoelectric element, and adhering soldering lugs with similar areas by using the viscosity of the soldering flux to finish the preparation of the soldering flux and the soldering lugs on the end surfaces of the p-type thermoelectric element and the n-type thermoelectric element; (2) placing the annular tray on the convex base; (3) enabling an inner ring electrode to abut against a boss of the convex base and be uniformly distributed on the annular tray, enabling end faces of the p-type thermoelectric element and the n-type thermoelectric element to alternately abut against the inner ring electrode according to p-type thermoelectric element and n-type and be uniformly distributed on the annular tray, enabling an outer ring electrode to abut against the other end faces of the p-type thermoelectric element and the n-type thermoelectric element and be staggered from the inner ring electrode and be uniformly distributed on the annular tray; (4) pushing the split clamping ring to the outer ring electrode from the edge of the boss base, placing the clamping ring on the clamping ring, and enabling the clamping ring to tightly press the inner ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the outer ring electrode by utilizing the gravity of the clamping ring to complete the assembly of the annular thermoelectric device; (5) the heating soldering lug is connected with the inner ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the outer ring electrode to complete the welding integration of the annular thermoelectric device; (6) and cooling to room temperature, taking down the pressure ring, removing the pressure ring, and lifting the annular tray to obtain the annular thermoelectric power generation device.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The embodiment is an annular thermoelectric power generation device designed according to a taper pipe part of an unmanned aerial vehicle exhaust pipeline (figure 2) with the temperature of 500 ℃;
the thermoelectric material of the annular thermoelectric power generation device adopts a filled skutterudite material, and n type is Yb0.3Co4Sb12P-type being Ce0.9Fe4Sb12The diversion electrodes (inner ring electrode and outer ring electrode) are made of nickel sheets, the electrodes and the thermoelectric material are connected through welding flux (made of silver-copper alloy sheets), and the thickness of a welding layer formed by the welding flux is 100 micrometers;
the structural form of the annular thermoelectric power generation device of the present embodiment is shown in fig. 3, an inner annular surface of the annular thermoelectric power generation device of the present embodiment is a high temperature end, and an outer annular surface thereof is a low temperature end;
the annular thermoelectric power generation device of the embodiment is composed of 21 p/n thermoelectric pairs in total, and the inner diameter of the annular thermoelectric power generation device is 52mm, wherein the p-type thermoelectric element and the n-type thermoelectric element are in an orthorhombic shape (figure 4), the inclination angle is 114.65 degrees, the cross section dimension is 3 x 3mm, and the thickness is 2 mm;
the length of an inner ring electrode of the annular thermoelectric power generation device is 6.5mm, and the folding angle is 170 degrees; the length of the outer ring electrode is 7mm, and the folding angle is 170 degrees;
when the ring-shaped thermoelectric power generation device is integrated, p-type thermoelectric elements and n-type thermoelectric elements are alternately arranged along the radial direction and are connected along the inner ring electrode and the outer ring electrode by using solder.
Example 2
The embodiment is an annular thermoelectric power generation device designed according to a straight pipe part of an unmanned aerial vehicle exhaust pipeline heat source (figure 2) with the temperature of 500 ℃ and the diameter of phi 56.6;
the ring-shaped thermoelectric power generation device of the embodiment adopts the same thermoelectric materials and electrodes as those of the embodiment 1;
the structural form of the annular thermoelectric power generation device of the present embodiment is shown in fig. 5, an inner annular surface of the annular thermoelectric power generation device of the present embodiment is a high temperature end, and an outer annular surface thereof is a low temperature end;
the straight tube is a special case of the taper tube, which is equivalent to the inclination angle equal to 90 degrees, and the thermoelectric element of the annular thermoelectric power generation device of the embodiment is changed from an orthorhombic body to a cubic body. According to design calculation, the annular thermoelectric power generation device of the embodiment is composed of 22 p-type thermoelectric elements and n-type thermoelectric element pairs in total, the inner diameter of the annular thermoelectric power generation device is 56.6mm, the cross-sectional dimension of the p-type thermoelectric elements and the n-type thermoelectric elements is 3 x 3mm, and the thickness of the annular thermoelectric power generation device is 2.5 mm;
the inner ring electrode and the outer ring electrode of the annular thermoelectric power generation device of the embodiment have the folding angle of 173.75 degrees (figure 6), and the lengths are 6.5mm and 7mm respectively;
in the case of the ring-shaped thermoelectric power generation device of this embodiment, p-type thermoelectric elements and n-type thermoelectric elements are alternately arranged in the radial direction and connected to the inner ring electrode and the outer ring electrode with solder.
Example 3
In this example, for a tubular heat source (FIG. 2) having an outer wall temperature of-500 ℃ and an outer diameter of phi 56.6 mm:
(1) thermoelectric element preparation
Adopts a filled skutterudite thermoelectric material, and n type is Yb0.3Co4Sb12P-type being Ce0.9Fe4Sb12. Firstly, synthesizing and preparing filled skutterudite powder, then sintering the filled skutterudite powder into a block material, cutting the block material into pieces with the thickness of 2.5mm, preparing a barrier layer (the material is Ti, and the thickness is 150 mu m) and a welding-assistant layer on the upper surface and the lower surface of the block material, cutting the block material into particles with the size of 3 multiplied by 2.5mm, and finally coating soldering flux and pasting a silver-copper alloy soldering piece (the thickness is 100 mu m) for later use;
(2) welding mould
The outer diameter of the heat source is the inner diameter of the annular device, correspondingly, the diameter of the convex base boss part is phi 56.6mm, the height is 10mm, and the diameter of the lower base can be designed and processed to be phi 72mm, and the height is 10 mm; the diameter of the outer ring of the annular tray is phi 74mm, and the height is 4 mm; the diameter of the inner ring of the clamping ring is phi 63.2mm, the inner ring is divided into 6 sections and numbered, and the parts are processed by high-strength graphite. The press ring is matched with the clamping ring, and the used material is 304 stainless steel;
(3) ring device assembly
The inner ring and the outer ring electrodes are all made of 0.3mm nickel sheets, the size of the inner ring electrode is 3 multiplied by 6.5 multiplied by 0.3mm, the size of the outer ring electrode is 3 multiplied by 7 multiplied by 0.3mm, the folded angle of the inner ring electrode is 173.75 degrees, and the folded angle of the outer ring electrode is 172.36 degrees; placing the annular tray on the convex base; an inner ring electrode is tightly attached to a boss of the convex base and is uniformly arranged on the annular tray, a p/n type filled skutterudite thermoelectric element is tightly attached to the inner ring electrode according to the p/n type alternate end face and is uniformly arranged on the annular tray, and an outer ring electrode is tightly attached to the other end face of the p/n type filled skutterudite thermoelectric element and is uniformly arranged on the annular tray in a staggered manner with the inner ring electrode; pushing the split clamping ring to the outer ring electrode from the edge of the boss base, placing the clamping ring on the clamping ring, and enabling the clamping ring to tightly press the inner ring electrode, the p/n type thermoelectric element and the outer ring electrode by utilizing the gravity of the clamping ring to complete the assembly of the annular thermoelectric device;
(4) ring shaped device welding integration
Placing the assembled annular filled skutterudite thermoelectric device and a mould in a hot pressing furnace, vacuumizing, filling argon, heating to 670 ℃, pressurizing to 12KN, keeping the temperature for 40 minutes, and connecting a hot welding sheet with the inner ring electrode, the p/n type thermoelectric element and the outer ring electrode to complete the welding integration of the annular thermoelectric device; and then the power is cut off and the temperature is reduced to below 50 ℃, the pressure is removed, the device and the mould are taken out, the pressure ring is taken down, the pressure ring is unloaded, the annular tray is lifted, and the filled skutterudite annular thermoelectric power generation device is obtained.
Example 4
In this example, for a tubular heat source (FIG. 2) having an outer wall temperature of 250 ℃ and an outer diameter of phi 56.6 mm:
(1) thermoelectric element preparation
Adopts bismuth telluride-based thermoelectric material, and n type is Bi2Sb2.7Te0.3P type is Bi0.5Sb1.5Te3. Cutting a zone-melting crystal bar into pieces with the thickness of 2.5mm, preparing Ni layers as a barrier layer and a welding-aid layer (the thickness is 20 mu m) on the upper surface and the lower surface of each piece, cutting the pieces into particles with the size of 3 multiplied by 2.5mm, and finally coating the welding-aid agent and sticking lead-tin alloy welding pieces (the thickness is 100 mu m) for later use;
(2) welding mould
The dimensions of the convex base, the annular tray and the clamping ring are the same as those of the embodiment 1, and the convex base, the annular tray and the clamping ring are made of aluminum alloy. The dimensions and materials of the pressure ring are the same as those of the embodiment 1;
(3) ring device assembly
The inner ring and the outer ring electrodes are all made of 0.3mm copper sheets, and the size and the folded angle of the copper sheets are the same as those of the copper sheets in the embodiment 1; the assembly steps of the ring-shaped device are the same as those of embodiment 1;
(4) ring shaped device welding integration
Heating to 300 ℃ in the air of a heating platform, keeping the temperature for 30 seconds, and connecting a hot welding fusion sheet with the inner ring electrode, the p/n type thermoelectric element and the outer ring electrode to complete the welding integration of the annular thermoelectric device; and then, cutting off the power and cooling to room temperature, taking down the pressure ring, removing the pressure ring, and lifting the annular tray to obtain the bismuth telluride based annular thermoelectric power generation device.
Claims (10)
1. A preparation method of an annular thermoelectric power generation device is characterized by comprising the following steps:
coating soldering flux on two end faces of the p-type thermoelectric element and the n-type thermoelectric element for bonding soldering lugs;
after the annular tray is placed on the convex base, the inner ring electrodes are distributed on the annular tray and abut against the bosses of the convex base;
one end faces of the p-type thermoelectric elements and the n-type thermoelectric elements are alternatively and circularly abutted against the inner ring electrode according to the p-type thermoelectric elements and the n-type thermoelectric elements;
the outer ring electrode is abutted against the other end faces of the p-type thermoelectric element and the n-type thermoelectric element and is arranged in a staggered manner with the inner ring electrode;
pushing the clamping ring with the split part with the chamfer at the upper part of the outer ring from the edge of the boss base to the outer ring electrode, placing the pressing ring on the clamping ring, and enabling the clamping ring to tightly press the outer ring electrode, the p-type thermoelectric element, the n-type thermoelectric element and the inner ring electrode by utilizing the gravity of the pressing ring to complete the assembly of the annular thermoelectric power generation device;
and heating the soldering lug to obtain the annular thermoelectric power generation device.
2. The production method according to claim 1, wherein the p-type thermoelectric element and the n-type thermoelectric element are made of at least one material selected from a bismuth telluride-based thermoelectric material, a lead telluride-based thermoelectric material, a transition metal oxide thermoelectric material, a half heusler thermoelectric material, a skutterudite-based thermoelectric material, a silicon germanium-based thermoelectric material, and a copper-based compound thermoelectric material.
3. The method according to claim 1, wherein the p-type thermoelectric element and the n-type thermoelectric element have a square, rectangular or rhombohedral structure, and the inclination angle of the rhombohedral structure is determined by the taper of the heat source; the dimensions of the p-type thermoelectric element and the n-type thermoelectric element are length × width × height = (3 mm to 5mm) × (2 mm to 5 mm).
4. The production method according to any one of claims 1 to 3, wherein the angle of folding of the inner-ring electrode in the direction along the center line between the p-type thermoelectric element and the n-type thermoelectric element is 150 ° to 175 °, and the angle of folding of the outer-ring electrode in the direction along the center line between the p-type thermoelectric element and the n-type thermoelectric element is 150 ° to 175 °.
5. The preparation method according to any one of claims 1 to 3, characterized in that the material of the soldering lug is any one simple substance or an alloy of any two substances of tin, gold, silver, copper, nickel and titanium, and the thickness of the soldering lug is 50 μm to 150 μm.
6. A producing method according to any one of claims 1 to 3, characterized in that barrier layers of at least one of Ni, Fe, Ti, Mo and Nb and alloys thereof and having a thickness of 20 μm to 150 μm are produced on both end faces of the p-type thermoelectric element and the n-type thermoelectric element before the flux is applied.
7. The production method according to any one of claims 1 to 3, wherein the material of the inner ring electrode and the outer ring electrode is selected from at least one of copper, iron, nickel, chromium, cobalt, titanium, molybdenum, tungsten, elemental niobium, and an alloy thereof.
8. The production method according to any one of claims 1 to 3, wherein the heating is performed by resistance heating or induction heating.
9. The production method according to any one of claims 1 to 3, wherein an angle of a chamfer of the clamp ring is 25 ° to 75 °.
10. The method of any one of claims 1-3, wherein the clamp ring is divided into 3 to 8 segments.
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